CN111647769B - Storage battery grid alloy and preparation method thereof - Google Patents
Storage battery grid alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a storage battery grid alloy and a preparation method thereof, belongs to the technical field of production of lead-acid storage batteries, and solves the problems that the existing grid alloy contains metallic calcium, is easy to oxidize to generate lead slag in the smelting process, and causes environmental pollution. The storage battery grid alloy provided by the invention comprises 0.5-5% of MAX phase ceramic material and the balance of pure lead; in the MAX phase ceramic material, M represents a transition metal element, A represents a Sn element, and X represents a carbon element; the preparation method of the storage battery grid alloy provided by the invention comprises the following steps: step 1, preparing MAX phase ceramic material by adopting a high-temperature microwave solid-phase synthesis method; step 2, preparing a master alloy ingot; and 3, forming the grid alloy. By adopting MAX phase material, the invention obviously reduces intergranular corrosion of the grid alloy, improves the structure of an alloy grain interface, and obviously improves the strength, corrosion resistance, creep resistance and the like of the alloy.
Description
Technical Field
The invention relates to the technical field of lead-acid storage battery production, in particular to a storage battery grid alloy and a preparation method thereof.
Background
The grid has the following functions in the lead-acid storage battery: a carrier supporting the active substance, serving as a carrier for the active substance; the current is conducted and collected, so that the current is uniformly distributed on the active substance. The quality of the grid directly affects the performance of various aspects of the battery, and therefore, the properties of the alloy making up the grid will directly affect the performance of the battery.
At present, the most common grid alloy used in industry is lead-calcium-tin-aluminum alloy, and the alloy has the greatest advantage of higher hydrogen evolution overpotential, so that the alloy has excellent maintenance-free performance. However, the presence of calcium element may cause formation of a calcium sulfate, lead oxide, or lead sulfate barrier layer having high resistivity at the interface between the active material and the grid, and cause PCL1 (quality Capacity Loss) effect at the initial stage of battery use, resulting in the end of the life of the battery.
Disclosure of Invention
In view of the above analysis, embodiments of the present invention are directed to provide a battery grid alloy and a preparation method thereof, so as to solve the problem that the existing grid alloy contains metallic calcium and is easily oxidized to generate lead slag during a smelting process, thereby causing environmental pollution.
The purpose of the invention is mainly realized by the following technical scheme:
on one hand, the invention provides a storage battery grid alloy, which comprises the following components in percentage by mass: 0.5-5% of MAX phase ceramic material and the balance of pure lead;
in the MAX phase ceramic material, M represents a transition metal element, A represents a Sn element, and X represents a carbon element.
Further, the MAX phase includes Ti2SnC、Ti3SnC2、TiSnC2、Zr2SnC、Zr3SnC2Or ZrSnC2One kind of (1).
On the other hand, the invention also provides a preparation method of the storage battery grid alloy, which is used for preparing the storage battery grid alloy and comprises the following steps:
step 1, preparing MAX phase ceramic material by adopting a high-temperature microwave solid-phase synthesis method;
adding M element metal simple substance powder, tin powder and graphite powder into a high-energy ball mill according to a molar ratio, performing ball milling mixing treatment, pressing the mixture into blocks by using a powder pressing machine, putting the block samples into a microwave sintering furnace for vacuum sintering, and synthesizing to obtain MAX phase ceramic materials;
step 2, preparing a master alloy ingot;
completely dissolving electrolytic lead in a smelting furnace, wrapping and pressing MAX phase ceramic materials into molten lead liquid by using a lead sheath, fully stirring to uniformly disperse the MAX phase ceramic materials, casting and cooling to obtain a master alloy ingot;
step 3, forming grid alloy;
dissolving the master alloy ingot and electrolytic lead in a lead melting furnace according to a required proportion, fully stirring to obtain a grid alloy, and molding the grid alloy by a plate casting machine to obtain the storage battery grid alloy.
Further, in the step 1, the particle diameters of the M element metal simple substance powder, the tin powder and the graphite powder are all 10-50 μ M.
Further, in the step 1, the rotating speed of the high-energy ball mill is 1000-2000 rpm, and the ball milling time is 1-3 h.
Further, in the step 1, the vacuum sintering temperature is controlled to be 700-1000 ℃, and the vacuum sintering time is 8-10 hours.
Further, in the step 1, the pressure of the powder pressing machine is 30-100 MPa, and the pressing time is 3-5 min.
Further, in the step 2, 50-60 parts of electrolytic lead is dissolved in a smelting furnace, the temperature of the smelting furnace is 550-580 ℃, 9-10 parts of MAX phase ceramic materials are wrapped by lead skins and pressed into molten lead liquid, 25-30 parts of electrolytic lead is added after stirring for 0.5-0.6 h, and the mixture is cast and molded after continuously stirring for 0.5-0.6 h and cooled.
Further, in the step 3, 50-60 parts of electrolytic lead is dissolved in a lead melting furnace, and the temperature of the lead melting furnace is 350-400 ℃.
Further, after electrolytic lead is dissolved to form a lead liquid, 9-10 parts of the master alloy ingot prepared in the step 2 is added into the molten lead liquid, stirring is carried out for 0.9-1 h, then 25-30 parts of electrolytic lead are added, and stirring is continued for 0.9-1 h, so that the grid alloy is obtained.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the invention adopts MAX phase ceramic material as grid material of lead-acid storage battery, and MAX phase comprises Ti2SnC、Ti3SnC2、TiSnC2、Zr2SnC、Zr3SnC2、ZrSnC2And the MAX phase ceramic material combines the high strength, high electric and thermal conductivity, corrosion resistance and oxidation resistance of metal and ceramic materials, and can meet the oxidation resistance requirement of the anode high potential on the grid.
(2) The invention adopts MAX phase ceramic material to replace the existing calcium element, obviously reduces intergranular corrosion of the grid alloy, improves the structure of an alloy grain interface, and obviously improves the strength, corrosion resistance, creep resistance and the like of the alloy. In addition, the MAX phase ceramic material adopted by the invention has excellent conductivity, can make the conductivity of the grid close to that of a pure lead grid, reduces the resistance of the battery in the charging and discharging processes, and improves the working efficiency.
(3) The existing grid alloy contains calcium element, the existence of the calcium element may cause the generation of a calcium sulfate, lead oxide or lead sulfate barrier layer with high resistivity at the interface between an active material and a grid, and PCL1 (quality Capacity Loss) effect is caused at the initial stage of the use of the battery, so that the service life of the battery is terminated; the grid alloy adopted by the invention does not add Ca element, so that a barrier layer cannot be formed, and simultaneously scum cannot be formed in the alloy preparation process to cause unbalance of the alloy component proportion.
(4) The grid alloy adopted by the invention has simple element composition and cannot generate any negative influence on the battery.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a graph showing the cycle life test of the battery grid alloy prepared in examples 1-4 and comparative example 1;
FIG. 2 is a schematic representation of the battery grid alloy prepared in example 1 after failure;
FIG. 3 is a schematic representation of a battery grid alloy prepared in example 2 after failure;
FIG. 4 is a schematic representation of a battery grid alloy prepared in example 3 after failure;
FIG. 5 is a schematic representation of a battery grid alloy prepared in example 4 after failure;
fig. 6 is a schematic diagram of the battery grid alloy prepared in comparative example 1 after failure.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The invention provides a storage battery grid alloy which comprises the following components in percentage by mass: 0.5-5% of MAX phase ceramic material and the balance of pure lead.
The MAX phase ceramic material is a novel metal ceramic functional material, wherein M represents transition metal elements, A represents Sn elements, and X represents carbon elements, and the microstructure of the MAX phase is in a hexagonal layered structure.
The MAX phase comprises Ti2SnC、Ti3SnC2、TiSnC2、Zr2SnC、Zr3SnC2、ZrSnC2Etc.; the MAX phase ceramic material combines the high strength, high electric and thermal conductivity, corrosion resistance and oxidation resistance of metal and ceramic materials, and the characteristics can meet the requirements of a positive electrode high potential to a plateThe grid has the requirement of oxidation resistance, and is very suitable to be used as a grid material of a lead-acid storage battery.
The invention adopts MAX phase material to replace the existing calcium element, obviously reduces intergranular corrosion of the grid alloy, improves the structure of an alloy grain interface, and obviously improves the strength, corrosion resistance, creep resistance and the like of the alloy.
The invention also provides a preparation method of the storage battery grid alloy, which comprises the following steps:
step 1, preparing MAX phase ceramic material by adopting a high-temperature microwave solid-phase synthesis method;
when a high-temperature microwave solid-phase method is adopted to synthesize the MAX-phase ceramic material, firstly, adding M element metal simple substance powder, tin powder and graphite powder into a high-energy ball mill according to a molar ratio, and pressing the mixture into blocks by using a powder pressing machine after ball milling and mixing, wherein the pressure of the powder pressing machine is 30-100 MPa, and the pressing time is 3-5 min; and putting the blocky sample into a microwave sintering furnace for vacuum sintering to obtain the synthesized MAX material.
In the step 1, the particle sizes of the M element metal simple substance powder, the tin powder and the graphite powder are 10-50 μ M; the particle sizes of the M element metal simple substance powder, the tin powder and the graphite powder are strictly controlled because: the particle size is too large, so that the dispersion of M element metal simple substance powder, tin powder and graphite powder in the alloy is not facilitated, slag inclusion is easily formed in the alloy, and the mechanical and chemical properties of the alloy are further influenced; and the particle size is too small, although the dispersion of the M element metal simple substance powder, the tin powder and the graphite powder in the alloy is better, the higher the corrosion resistance and the mechanical strength of the grid alloy are, but the higher the cost is.
The rotating speed of a high-energy ball mill in MAX material preparation is 1000-2000 rpm, and the ball milling time is 1-3 h; so as to ensure the full mixing of the M element metal simple substance powder, the tin powder and the graphite powder.
Step 2, preparing a master alloy ingot;
and dissolving 50-60 parts of electrolytic lead in a smelting furnace, wherein the temperature of the smelting furnace is 550-580 ℃, wrapping and pressing 9-10 parts of MAX phase ceramic material into molten lead liquid by using lead skin or lead foil, stirring for 0.5-0.6 h, adding 25-30 parts of electrolytic lead, continuously stirring for 0.5-0.6 h, and then casting, molding and cooling to obtain a master alloy ingot.
Step 3, forming grid alloy;
and (3) dissolving 50-60 parts of electrolytic lead in a lead melting furnace, wherein the temperature of the lead melting furnace is 350-400 ℃, adding 9-10 parts of the mother alloy ingot prepared in the step (2) into the molten lead after the electrolytic lead is dissolved to form a lead liquid, stirring for 0.9-1 h, then adding 25-30 parts of electrolytic lead, continuously stirring for 0.9-1 h to obtain an MAX grid alloy, and casting and molding the MAX grid alloy by using a plate casting machine to obtain the storage battery grid alloy.
The MAX phase-containing material is prepared by smelting, the MAX phase-containing material is prepared into the master alloy, and then the MAX phase grid alloy is obtained by diluting and smelting the master alloy, so that the MAX material is uniformly distributed in the alloy components, and the problem of local corrosion of the grid alloy is solved.
Example 1
The embodiment 1 provides a preparation method of a storage battery grid alloy, which comprises the following steps:
step 1, preparing Ti2SnC material;
ti powder, Sn powder and graphite powder are mixed according to a molar ratio of 2: 1: 1 into a high-energy ball mill, the average particle diameter of the powder is 50 μm, the rotation speed of the ball mill is set at 1500rpm, and the ball milling time is 2 h. Pressing and molding the ball-milled and mixed sample under the pressure of 30MPa for 3min, and performing vacuum sintering in a microwave sintering furnace at 700 ℃ for 8h to obtain Ti2SnC material.
Step 2, preparing Ti2SnC master alloy ingot;
dissolving 60 parts of electrolytic lead in a smelting furnace, keeping the temperature at 550 ℃, and adding 10 parts of Ti by using lead sheath2Pressing the SnC material into a smelting furnace, fully stirring for 0.5h, then adding 30 parts of electrolytic lead, continuously stirring for 0.5h, and finally casting into ingots to obtain Ti2Ti with SnC content of 10%2An SnC master alloy ingot.
Step 3, Ti2Molding SnC grid alloy;
60 parts of electrolytic lead were dissolved in a lead melting furnace, the temperature was maintained at 350 ℃, and then 10 parts of Ti was added2SnC master alloyAdding the ingot into the molten lead liquid, fully stirring for 1h, then adding 30 parts of electrolytic lead ingot, continuously stirring for 1h, and molding the grid alloy by a plate casting machine to obtain the storage battery grid alloy.
The MAX grid alloy provided by the invention has various performance indexes capable of meeting the use of a lead-acid storage battery grid due to the addition of MAX phase materials, and has the following performance advantages compared with the existing grid alloy:
firstly, the MAX material adopted by the invention has excellent conductivity, so that the conductivity of the grid is close to that of a pure lead grid, the resistance of the battery in the charging and discharging processes is reduced, and the working efficiency is improved.
Secondly, Ca element is not added in the grid alloy adopted by the invention, so that a barrier layer cannot be formed, and scum cannot be formed in the alloy preparation process to cause unbalance of the alloy component proportion.
Furthermore, the grid alloy adopted by the invention has simple element composition and does not have any negative influence on the battery.
In conclusion, the MAX material adopted by the invention has excellent oxidation resistance and corrosion resistance, and higher Young modulus, can inhibit the failure of the battery caused by the oxidation corrosion of the positive grid in the use process of the battery, and prolongs the service life of the lead storage battery.
Example 2
The embodiment 2 provides a preparation method of a storage battery grid alloy, which comprises the following steps:
step 1, preparing Ti3SnC2A material;
ti powder, Sn powder and graphite powder are mixed according to a molar ratio of 3: 1: 2 into a high-energy ball mill, the average particle size of the powder is 15 μm, the rotation speed of the ball mill is set to 1000rpm, and the ball milling time is 1 h. Pressing and molding the ball-milled and mixed sample under the pressure of 50MPa for 3min, and performing vacuum sintering in a microwave sintering furnace at 800 ℃ for 9h to obtain Ti2SnC powder.
Step 2, preparing Ti2SnC master alloy ingot;
60 parts of electrolytic lead are dissolved in a smelting furnace, the temperature is kept at 560 ℃, and 10 parts of Ti is added by lead sheath2Pressing the SnC material into a smelting furnace, fully stirring for 0.5h, then adding 30 parts of electrolytic lead, continuously stirring for 0.5h, and finally casting into ingots to obtain Ti2Ti with SnC content of 10%2An SnC master alloy ingot.
Step 3, Ti2Molding SnC grid alloy;
60 parts of electrolytic lead were dissolved in a lead melting furnace, the temperature was maintained at 370 ℃, and then 10 parts of Ti was added2Adding the SnC master alloy ingot into the molten lead liquid, fully stirring for 1h, then adding 30 parts of electrolytic lead ingot, continuously stirring for 1h, and forming the grid alloy by a plate casting machine to obtain the storage battery grid alloy.
Example 3
The embodiment 3 provides a preparation method of a storage battery grid alloy, which comprises the following steps:
step 1, preparing Zr2SnC material
Zr powder, Sn powder and graphite powder are mixed according to a molar ratio of 2: 1: 1 into a high-energy ball mill, the average particle size of the powder was 15 μm, the rotational speed of the ball mill was set at 1000rpm, and the milling time was 1 h. Pressing and molding the ball-milled and mixed sample by using the pressure of 70MPa, wherein the pressing time is 4min, and performing vacuum sintering for 9h at the temperature of 900 ℃ in a microwave sintering furnace to obtain Zr2SnC material.
Step 2, preparing Zr2SnC master alloy ingot;
60 parts of electrolytic lead are dissolved in a smelting furnace, the temperature is kept at 570 ℃, and 10 parts of Zr is added by lead sheath2Pressing the SnC material into a smelting furnace, fully stirring for 0.5h, then adding 30 parts of electrolytic lead, continuously stirring for 0.5h, and finally casting into ingots to obtain Zr2Zr with SnC content of 10%2An SnC master alloy ingot.
Step 3, Zr2Molding SnC grid alloy;
60 parts of electrolytic lead were dissolved in a lead melting furnace, the temperature was maintained at 380 ℃, and then 10 parts of Zr2Adding SnC master alloy ingot into molten lead liquid, fully stirring for 1h, adding 30 parts of electrolytic lead ingot, continuously stirring for 1h, and forming the grid alloy by a plate casting machineAnd obtaining the accumulator grid alloy.
Example 4
The embodiment 4 provides a preparation method of a storage battery grid alloy, which includes the following steps:
step 1, preparing ZrSnC2Material
Zr powder, Sn powder and graphite powder are mixed according to a molar ratio of 1: 1: 2 into a high-energy ball mill, the average particle size of the powder is 15 μm, the rotation speed of the ball mill is set to 1000rpm, and the ball milling time is 1 h. Pressing and molding the ball-milled and mixed sample under the pressure of 100MPa for 5min, and performing vacuum sintering in a microwave sintering furnace at 1000 ℃ for 10h to obtain ZrSnC2A material.
Step 2, preparing ZrSnC2A master alloy ingot;
dissolving 60 parts of electrolytic lead in a smelting furnace, keeping the temperature at 580 ℃, and using a lead sheath to dissolve 10 parts of ZrSnC2Pressing the material into a smelting furnace, fully stirring for 0.5h, then adding 30 parts of electrolytic lead, continuously stirring for 0.5h, and finally casting into ingots to obtain ZrSnC2ZrSnC with content of 10%2A master alloy ingot.
Step 3, ZrSnC2Forming grid alloy;
60 parts of electrolytic lead were dissolved in a lead melting furnace, the temperature was maintained at 400 ℃, and then 10 parts of ZrSnC2And adding the mother alloy ingot into the molten lead liquid, fully stirring for 1h, then adding 30 parts of electrolytic lead ingot, continuously stirring for 1h, and forming the grid alloy by a plate casting machine to obtain the storage battery grid alloy.
Comparative example 1
The comparative example 1 provides a silver alloy positive grid for a lead-acid storage battery, which comprises the following components in percentage by weight: 0.08 to 0.15 percent of Ca, 0.01 to 0.05 percent of Al, 0.8 to 1.5 percent of Sn, 0.005 to 0.02 percent of Ag, 0.02 to 0.08 percent of Bi, 0.01 to 0.08 percent of Se and the balance of Pb.
The comparative example also provides a preparation method of the silver alloy positive grid for the lead-acid storage battery, which specifically comprises the following steps:
step 1, respectively weighing Ca, Al, Sn, Ag, Bi and Se with corresponding mass according to the raw material composition of the positive grid alloy for the lead-acid storage battery; the positive grid alloy for the lead-acid storage battery comprises the following raw materials: ca: 0.08-0.15%, Al: 0.01-0.05%, Sn: 0.8-1.5%, Ag: 0.005-0.02%, Bi: 0.02-0.08%, Se: 0.01 to 0.08 percent of the total weight of the alloy, and the balance of Pb;
step 2, heating the electrolytic lead to 400-550 ℃ in a lead pot to melt the electrolytic lead to prepare lead liquid;
step 3, adding the Ca and the Al weighed in the step 1 into 85-95% of the lead liquid obtained in the step 2, and completely melting at 500-600 ℃ to form Pb-CaAl master alloy melt; adding the Bi and Se weighed in the step 1 into the rest part of the lead liquid, completely melting at 450-550 ℃, and uniformly mixing to form alloy mixed melt;
step 4, sequentially pouring the Pb-Ca-Al master alloy melt and the alloy mixed melt obtained in the step 3 into a lead pot, adding the Sn and the Ag weighed in the step 1, smelting and mixing at the temperature of 500-550 ℃, slowly stirring to be uniform, and casting to form to obtain the positive grid alloy for the lead-acid storage battery;
and 5, storing the cast positive grid alloy for the lead-acid storage battery for one week at normal temperature, and performing age hardening to obtain the lead-acid storage battery.
The calcium alloy of the comparative example 1 contains metallic calcium, and needs to be smelted at a temperature of more than 600 ℃, and due to the excessively high temperature, a large amount of lead fume is generated in a lead smelting pot, and lead slag is easily oxidized in the smelting process, so that the calcium alloy is not beneficial to energy conservation and environmental protection. The specific resistance of the grid alloys prepared in comparative example 1 and examples 1 to 5 is shown in table 1 below.
Table 1 comparison of properties of grid alloys prepared in examples 1-5, comparative example 1
As can be seen from Table 1, the practice of the inventionThe storage battery grid alloy prepared in examples 1-4 has an aged Brinell hardness of 17-19, which is greater than that of the silver alloy positive grid prepared in comparative example 1, and the resistivity of the grid alloy is 2.32-2.40.10-7Omega. m, and the resistivity of the grid alloy of comparative example 1 was 2.53. multidot.10-7Omega.m, which is significantly greater than the resistivity of the grid alloy prepared by the invention.
In addition, as can be seen from fig. 1, five batteries of the grid alloy prepared in examples 1 to 4 of the present invention and the silver alloy positive grid prepared in comparative example 1 were analyzed and compared after failure, and the cycle number of the grid alloy in examples 1 to 4 was 298 to 353; among them, the number of cycles of the silver alloy positive grid in example 1 was 338 times, example 2 was 333 times, example 3 was 353 times, and example 4 was 298 times, whereas the number of cycles of the silver alloy positive grid in comparative document 1 was only 222 times. Therefore, the service life of the storage battery prepared by the grid alloy is obviously shorter than that of the storage battery prepared by the grid alloy prepared by the invention.
The case after the failure of the grid alloy prepared in example 1 is shown in fig. 2, the case after the failure of the grid alloy prepared in example 2 is shown in fig. 3, the case after the failure of the grid alloy prepared in example 3 is shown in fig. 4, the case after the failure of the grid alloy prepared in example 4 is shown in fig. 5, the case after the failure of the silver alloy positive grid prepared in comparative example 1 is shown in fig. 6, and it can be known by comparing fig. 2 to 6 that the service life of the silver alloy positive grid prepared in comparative example 1 is short due to serious intergranular corrosion and damage after the failure of the silver alloy positive grid; the grid alloy in the embodiments 1-4 of the invention has good corrosion resistance and long service life.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. The battery grid alloy is characterized by comprising the following components in percentage by mass: 0.5-5% of MAX phase ceramic material and the balance of pure lead;
in the MAX phase ceramic material, M represents a transition metal element, A represents a Sn element, X represents a carbon element, and the MAX phase comprises Ti2SnC、Ti3SnC2、TiSnC2、Zr2SnC、Zr3SnC2Or ZrSnC2One kind of (1).
2. A method for preparing a battery grid alloy of claim 1, comprising the steps of:
step 1, preparing MAX phase ceramic material by adopting a high-temperature microwave solid-phase synthesis method;
adding M element metal simple substance powder, tin powder and graphite powder into a high-energy ball mill according to a molar ratio, performing ball milling mixing treatment, pressing the mixture into blocks by using a powder pressing machine, putting the block samples into a microwave sintering furnace for vacuum sintering, and synthesizing to obtain MAX phase ceramic materials;
step 2, preparing a master alloy ingot;
completely dissolving electrolytic lead in a smelting furnace, wrapping and pressing MAX phase ceramic materials into molten lead liquid by using a lead sheath, fully stirring to uniformly disperse the MAX phase ceramic materials, casting and cooling to obtain a master alloy ingot;
step 3, forming grid alloy;
dissolving the master alloy ingot and electrolytic lead in a lead melting furnace according to a required proportion, fully stirring to obtain a grid alloy, and molding the grid alloy by a plate casting machine to obtain the storage battery grid alloy.
3. The method for preparing the battery grid alloy according to claim 2, wherein in the step 1, the particle sizes of the M element metal simple substance powder, the tin powder and the graphite powder are all 10-50 μ M.
4. The preparation method of the battery grid alloy according to claim 3, wherein in the step 1, the rotation speed of the high-energy ball mill is 1000-2000 rpm, and the ball milling time is 1-3 h.
5. The preparation method of the battery grid alloy according to claim 2, wherein in the step 1, the vacuum sintering temperature is controlled to be 700-1000 ℃, and the vacuum sintering time is 8-10 hours.
6. The preparation method of the battery grid alloy according to claim 2, wherein in the step 1, the pressure of the powder pressing machine is 30-100 MPa, and the pressing time is 3-5 min.
7. The preparation method of the grid alloy for the storage battery of claim 2, wherein in the step 2, 50-60 parts of electrolytic lead are dissolved in a smelting furnace, the temperature of the smelting furnace is 550-580 ℃, 9-10 parts of MAX phase ceramic materials are wrapped and pressed into molten lead liquid by lead skins, 25-30 parts of electrolytic lead are added after stirring for 0.5-0.6 h, and casting molding and cooling are carried out after continuous stirring for 0.5-0.6 h.
8. The preparation method of the battery grid alloy according to claim 2, wherein 50-60 parts of electrolytic lead is dissolved in a lead melting furnace in the step 3, and the temperature of the lead melting furnace is 350-400 ℃.
9. The preparation method of the grid alloy of the storage battery according to claim 8, wherein 9-10 parts of the mother alloy ingot prepared in the step 2 is added into the lead liquid after the electrolytic lead is dissolved to form the lead liquid, the mother alloy ingot is stirred for 0.9-1 hour, then 25-30 parts of the electrolytic lead are added, and the grid alloy is obtained after the stirring is continued for 0.9-1 hour.
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